CA2136997A1

CA2136997A1 - Thiadiazolines

Info

Publication number: CA2136997A1
Application number: CA 2136997
Authority: CA
Inventors: Peter Muller; Heinz-Jurgen Wroblowsky; Klaus Lurssen; Hans-Joachim Santel; Robert R. Schmidt
Original assignee: Individual
Current assignee: Bayer AG
Priority date: 1992-06-02
Filing date: 1993-05-19
Publication date: 1993-12-09
Also published as: AU4314093A; JPH07507282A; WO1993024474A1; EP0643707A1; DE4218157A1

Abstract

Thiadiazolines A b s t r a c t The invention relates to new thiadiazolines of the general formula (I)

Description

7t~ nn~
~F T~ I ,?~ 3 ~

; The invention relates to new thiadiazolines, to a process for their preparation, and to their use-as herb~cides.

It has been disclosed that certain thiadiazolines, such ~ as, for example, 2-methyl~no-3-benzyl-5-(3-chloro-1 5 phenyl)-~4- 1 ~ 3,4-thiadiazolirle, have herbicidal j prope.rties (af. D~-OS (German Published Speci~ication) ~ 2717742; cf. also US Patent 40'20078, US Patent 4104053).
i ~owever, the herbicidal activit:y of these known compounds and their crop plant tolerance are not always satisfactory.

The new thiadiazolines of the general formula (I) have now been found, ,CH2 ~ tR3)n (I) R 1 J~S~N - R2 in which n represents the number 0, 1, 2 or 3, ¦ 15 Rl represents Cl-C6-alkyl which is optionally substi-tuted by halogen or Cl-C4-alkoxy, or represents C3-C6-cycloalkyl or C3-C6-cycloalkyl-Cl-C2-alkyl, in each case optionally substituted by halogen and/or Cl-C4-alkyl, or represents phenyl, fluorophenyl, difluorophenyl, 2-chlorophenyl, 4-chlorophenyl, bromophenyl, nitrophenyl, cyanophenyl, 2-methyl-phenyl, 4-methylphenyl, trifluoromethylphenyl, Le A 29 158-PCT

~ 36997 , .~
. - 2 -chlorodifluoromethylphenyl, fluorodichloromethyl-phenyl, bi~-trifluorometllylphenyl, ethylphenyl, propylphenyl, isopropylphenyl, tert-butylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, pro-S poxyphenyl, isopropoxyphQnyl, methylthiophenyl, ethylthiophenyl, methyl~ulphinylphenyl, ethyl-sulphinylphenyl, methyl~ulphonylphenyl, ethyl-sulphonylphenyl, difluoromethoxyphenyl, trifluoro-methoxyphenyl, difluoromethylthiophenyl, trifluoro-methylthiophenyl, or represents furyl, tetrahydro-furyl, thienyl, tetrahydrothienyl or pyridyl, in each case optionally substituted by halogen, Cl-C4-alkyl and/or Cl-C4-halogenoalkyl, R2 represents Cl-C6-alkyl and R3 represe~ts halogen, cyano, nitro, carboxyl, carbamoyl, or represents Cl-C4-alkyl, C,-C4-alkoxy or C,-C4-alkoxy-carbonyl, in each case optionally substituted by halogen.

The new thiadiazolines of the general formula (I) are obtained when thiadiazoles of the general formula (II) N___N
Rl ~ s ~ N~_R2 ~II) in which R' and R2 have the abovementioned meaning, Le A 29 158-PCT

'. ' , ` ' . ' ' : ,-, ` ` , . . ' , ' !

-- 3 -- .
are reacted with aralkyl halides of the general formula (III) -X-CH2 ~ (R3)n tIII) in which ~.

n and R3 have the abovementioned meaning and X represents halogen, in psrticular chlorine or bromine~

if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent.
, The new thiadiazolines of the general formula (I) are :
di~tinguished by powerful herbicidal activity. ~ .

Surprisingly, the compounds of the formula (I) according to the invention show a considerably more powerful activity against a series of problem weeds than the known ~:
compound 2-methylimino-3-benzyl-5-(3-chlorophenyl)-~
1,3,4-thiadiazoline, which is chemically similar and an :
active compound of the same direction of action, while :
being well tolerated by crop plants such as, for example, wheat and, in ~ome cases, also beet.

The invention preferably relates to compounds of the ~ 20 formula (I) in which Le A 29 158-PCT

36~97 _ 4 _ n represents tha number O, 1, 2 or 3, Rl represents C,-C4-alkyl which i9 optionally su~sti~
tuted by fluorine, chlorine, bromine, methoxy or ethoxy, or represents C3-C6-cycloalkyl or C3-C6-cycloalkyl-C1~C2-alkyl, in each case optionally substituted by fluorine, ~hlorine, bromine, meth~l, ethyl, propyl or isopropyl, or represents phenyl, 2-, 3- or 4-fluorophenyl, 2,3-, 2,4-, 2,5-, 3,4-, 3,5- or 2,6-difluorophenyl, 2 chloro- or 4-chloro-phenyl, 4-bromophenyl, 2-, 3- or 4-nitrophenyl, 2-, 3- or 4-cyanophenyl, 2-methyl- or 4-methylphenyl, 2-, 3- or 4-trifluoromethylphenyl, 3,5-bis-tri-fluoromethylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 2-, 3- and 4-methoxyphenyl, 3,4-dimethoxyphenyl, 4-ethoxy-phenyl,4-methylthiophenyl,4-methylsulphonylphenyl, 2- and 4-difluoromethoxyphenyl, 2- and 4-trifluoro-methoxyphenyl, or represents furyl, thienyl or pyridyl, R2 repre~ents C,-C3-alkyl and R3 represents fluorine, chlorine, bromine, cyano, nitro, carboxyl or carbamoyl, or represents C1-C3-alkyl, C,-C3-alkoxy or C,-C3-alkoxy-carbonyl, in each case optionally substituted by fluorine or chlorine.

In particular, the invention relates to compounds of the formula (I) in which n represents the number 0, 1 or 2, Le A 29 158-PCT

.,.. , . . ~ , . .. .. , , -, ,, . . , , . -., - . . , : , 69'37 represents methyl, ~thyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl r chloromethyl, fluoromethylS dichloromethyl, difluoromethyl, tri-chloromethyl,trifluoromethyl,chlorodifluoromethyl, fluorodichloromethyl, chloroethyl, fluoroethyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxy-ethyl, cyclopropyl, dichlorocyclopropyl, dimethyl-cyclopropyl, cyclopentyl, cyclohexyl, phenyl, 2-, 3-or 4-fluorophenyl, 2,3-, :2,4-, 2,5-, 3,4-, 3,5- or 2,6-difluorophenyl, 2~chloro- or 4-chlorophenyl, :~
4-bromophenyl, 2-, 3- or 4-nitrophenyl, 2-, 3- or 4-cyanophenyl, 2-methyl or 4-methylphenyl, 2-, 3-or4-trifluoromethylphenyl,3,5-bis-trifluoromethyl- ~ .
phenyl, 2-, 3- or 4-methoxyphenyl, furyl or thienyl, ` `:. ' R2 represents methyl and ;

R3 represents fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, trifluoromethyl, methoxy or ethoxy.
.
Alky~ - also in conjunction with hetero atoms, ~uch as, for example, alkoxy - represents in each case straight-chain or branched alkyl, even where this is not mentioned expressly.

Halogen in each case represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine. :

~ The definitions of radicals mentioned above, either in general or in preferred ranges, apply to the end products Le A 29 158-PCT

;

~ ~ 36~97 ! - 6 of the formula (I) and, analogously, to the starting substances required for their preparat on. These defi-nitions of radicals can be co~mbined with each other as desired, that is to say combinations between the pre-ferred ranges are also possible.

If, for example, 2-isopropyl~-5-methylamino-1,3,4-thia-diazole and 2-fluoro-benzyl chl.oride are used as starting substances, the course of the reaction in the proces~
according to the invention can be outlined by the follow-ing equation:

N-__N
tC~3)2CH ~ S ~ N~CH3 ~ C1-C~

¦ F
-HCl ~CH3)2CH'~S ~ ~CH3 The thiadia~oles of the general formula (II) to be used as starting substances are known and/or can be prepared by known processes (cf. US Patent 3522267, DE-OS (German Published Specification) 1816696, DE-QS (German Published Specification) 2100057, DE-OS (German Published Specification) 2231664, DE-OS (German Published Specifi-cation) 2247330, DE-OS (~erman Published Specification) 2440922, DE-OS (German Published Specification) 2541115, DE-OS (German Published Specification) 2545142, US Patent 4028090, US Patent 4092148, US Patent 4283543, US Patent 4686294 and EP-A 296864).

Le A 29 158-PCT

~1 36~97 ~: `

The aralkyl halides of the formula (III) furthermore to be used as starting substances are known chemicals for organic synthesis.

The process according to the invention for the prepa-ration of the new thiadiaæolines of the formula (I) is preferably carried out using diluents. Suitable diluents are all inert organic solvents. The~e preferably include aliphatic and aromatic, optionally halogenated hydro-carbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloro-form, carbon tetrachloride, chlorobenzene and o-dichloro-benzene, ethers, such as diethyl ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetra-hydrofuran and dioxane, ketones such as acetone, methylethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, esters, such as methyl acetate and ethyl acetate, nitriles, such as for example, acetonitrile and propio-nitrile, amides, such as, for example, dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone, and also dimethyl sulphoxide, tetramethylene sulphone and hexa-methylphosphoric triamide.

Acid acceptors which can be employed in the process according to the invention are all acid-binding agents which can conventionally be used for such reactions. The ~ollowing are preferably suitable: alkali metal hydrides and alkaline earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal hydroxides and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, Le A 29 158-PCT

~13~97 :~ `

potassium hydroxide and calcium hydroxide, alkali metal carbonates, alkali metal hydrogen carbonates, alkaline earth metal carbonates and alkaline earth metal hydrogen carbonates, such as sodium cc-!rbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate and calcium carbonate, alkali metal acetates, such as sodium acetate and E~otassium acetate, alkali metal alcoholates, such as sodium methylate, sodium ethylate, sodium propylate, sodium isopropylate, sodium butylate, sodium isobutylate, sodium tert-butylate, potassium methylate, potassium ethylate, potassium propylate, potassium isopropylate, potassium butylate, potassium isobutylate and potassium tert-butylate, further basic nitrogen compounds, such as trimethylamine, triethylamine, tripropylamine, tributylamine, diisobutyl-amine, dicyclohexylamine, ethyldiisopropylamine, ethyldi-cyclohexylamine, N,N-~imethylbenzylamine, N,N-dimethyl-aniline, pyridine, 2-methyl~, 3-methyl-, 4-methyl-, 2,4-dimethyl~, 2,6-dimethyl-, 2-ethyl-, 4-ethyl- and 5-ethyl-2-methyl-pyridine, 1,5-diazabicyclo-t4,3,0]-non-5 ene (DBN), 1,8-diazabiayclo-~5,4,0]-undec-7-ene (DBU) and 1,4-diazabicyclo-[2,2,2]-octane (DABC0).

When carrying out the process according to the invention, the reaction temperatures can be varied within a substan-tial range. In general, the process is carried out at temperatures between 0C and 200C, preferably at tem-peratures between 20C and 150C.

The process according to the invention is generally carried out under a~mospheric prPssure. ~owever, it is also possible to carry out the process under elevated or :`

Le A 29 158-PCT

` ~13~997 .. g reduced pressure.

To carry out the process according to the invention, the st-axting substances required in each case are generally employed in approximately equimolar amounts. However, it is al o possible to employ one of the two components employed in each case in a larger excess. The reactions are generally carried out in a suitable diluent, if appropriate in the presence of an acid acceptor, and the reaction mixture is stirred for several hours at the temperature required in each case. Working-up in the process according to the invention is carried out in each case by customary methods (cf. the Preparation Examples).

ThP active compounds according to the invention can be used as defoliants, desiccants, agents for destroying broad-leaved plant~ and, e~pecially, as weed-killers. By weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are undesired. Whether the ~ubstances according to the invention act as total or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, for example, in connection with the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, ~anthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Le A 29 158-PCT

~ 1 3 ~ 9 9 7 --. 10 --Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Cent~urea, Trifolium, Ranunculus and Taraxacum.

Dicotyledon cultures of the qenera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera~

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
:.: .
However, the use of the active compounds according to the invention i~ in no way restricted to these genera, but also extends in the same manner to other plants.

The compounds are suitable, depending on the concen-tration, for the total combating of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for combating weeds in perennial cultures, for example afforestations, deco-rative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee Le A 29 158-PCT

~136997 plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, sof~ fruit plantings and hopfields, in lawns, turf and pasture-land, and for the selective combating of weecls in annual cultures.

The compounds of the formula (I) according to the inven-tion are suitable, in particular, for selectively combat-ing dicotyledon weeds in monocotyledon and dicotyledon cultures, mainly by the pre-emergence method.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspension~, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concen-trates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.

These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvent~ and/or solid carriers, optionally with the use of surface-active agents, that is emulsify-ing agents and/or dispersing agents and/or foam-forming agents.

In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As lîquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkylnaphtha-lenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as Le A 29 158-PCT

- ' cyclohexane or paraffins, ~or example petroleum frac-tions, mineral and veg~table oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, Ruch as acetone~ methyl ethyl ketone, methyl iso~utyl ketone or cyclohexanone, strongly polar sol-vents, such as dimethylformamide and dimethyl sulphoxide, as well as water.

As solid carriers there are suitable: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, mont-morillonite or diatomaceous earth, and gxound synthetic minerals, such as highly disperse silica, alumina and silicates; as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as caicite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks;
as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethy-lene fatty alcohol ethers, for example alkylaryl poly-glycol ethers, alkylsulphonates, alkyl sulphates, aryl-sulphonates a~ well as albumen hydrolysis products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such ~:' '`:, Le A 29 158-PCT

~1~6~97 i ~

as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Further-additives can be mineral and vegetable oils.

It is possible to use colorants such as inorganic pig-ments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dye-stuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90~.

For combating weeds, the active compounds according to the invention, as such or in the form of their formu-lations, can also be u~ed as mixtures with knownherbicides, finished formulations or tank mixes being possible .

Suitable herbicides for the mixtures are known herbi-cides, for example anilides such as, for example, diflu-fenican and propanil; arylcarboxylic .acids such as, forexample, dichloropicolinic acid, dicamba and .picloram;
aryloxyalkanoic acids such as, for example, 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr;
aryloxy-phenoxy~alkanoic esters such as, for example, diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; azinones such as, for example, chloridazon and norflurazon; carbamates such as, for examp:Le, chlorpropham, desmedipham, phenmedipham Le A 29 158-PCT

~ ~36 997 : .

and propham; chloroacetanilides such as, for example, alachlor, acetochlor, butachlor, meta~achlor, metola-j chlor, pretilachlor and propachlor; dinitroanilines such ¦ as, for example, oryzalin; pendimethalin and trifluralin;
¦ 5 diphenyl ethers such as, for example, acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; ureas such as~ for example, chlor-toluron, diuron, fluometuron, isoproturon, linuron and methabenzthiazuron; hydroxylamines such as, for example, alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim; Lmidazolinones such as, for example, imazethapyr, imazamethabenz, imazapyr and imazaquin;
nitriles such as, for example, bromoxynil, dichlobenil and ioxynil; oxyacetamides such as, for example, mefenacet; sulphonylureas such as, for example, amido-sulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlor-sulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; thiocar-bamates such as, for example, butylate, cycloate, di-allate, EPTC, esprocarb, molinate, prosulfocarb, thioben-carb and tri-allate; triazines such as, for example, atrazine, cyanazine, simazine, simetryn, terbutryn and terbutylazine; triazinones such as, for example, hexa-zinone, metamitron and metribuzin; others such as, for example, aminotriazole, ~enfuresate, bentazone, cin-methylin, clomazone, clopyralid, difenzoquat, dithiopyr, ethofumesate, fluorochloridone~ glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.
' Mixtures with other known active compounds, such as Le A 29 158-PCT ;

~i"''`,'','''''"'"''`,',.''','"'',`'''''''`"' '' 136~97 - 15 - ~
fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents w~ich improve soil structure, are also possible.

The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules.
They are used in the customary manner, for example by watering, spraying, atomizing or scattering.

The active compounds according to the invention can be applied either before or after emergence of the plants.

They can also be incorporated into the soil before sowing.

The amount of active compound used can vary within a relatively substantial range. It depends essentially on the nature of the de~ired effect. In general, the amounts used are between 1 g and 10 kg of active compound per heatare of soil surface, preferably between 5 g and 5 kg per ha.

The preparation and use of the active compounds according to the invention can be seen from the following examples.

Le A_29 158-PCT

'.~'`.' :'. ' ' : ' ' ' ' . ' ' ' . . ' ' ' ,~ ~1.36g97 Preparation ~xamples:

Example 1 ,CH2~F

~ S ~ -C~3 A mix~ure of 4.0 g (21 mmol) of 2-methylamino-5-phenyl-1,3,4-thiadiazole, 6.1 g (42 mmol) of 4-fluoro-benzyl chloride and 100 ml of dioxane is refluxed for 8 hours.
After cooling, it is diluted with 200 ml of hexanè and subjected to filtration with suction. The ~ilter cake is washed with diethyl ether and dried and then stirred with 45 ml of 10~ strength potassium hydroxide solution in methanol, and the mixture is refluxed for 2 hours. The product, which is obtained in crystalline form after cooling, is isolated by filtration with suction.

4.3 g (68% o~ theory~ of 2-methylimino-3-(4-fluoro-benzyl)-5-phenyl-~4-1,3,4-thiadiazoline of melting point 78C are obtained.

Other examples of the compounds of the formula (I) which can be prepared analogously to Example 1 and following the general description of the preparation process according to the invention are those listed in Table 1 jbelow. ~-~

Le A 29 158-P~T

~` ~136997 .i1 . - ,.:
;l -- 1 7 -- ;

~CHz~R3)~ -Rl S~bN-R2 Table 1 Examples of the compounds of the f ormula ( I ) Ex. n Rl R2 (Po~ition-)R3 Melting No . point ( C ) __ 2 0 ~ CH3 - (amo~phous) 3 1 y CH3(4- ~C1 6z 4 0 ~ CH3 - 5 6 F2CHS ., 5 1 ~ 3 CH3 (4-)Cl s~ :

, Le A 29 158-PCT

,.. ~ ,...................... . , . - . .

..,."~",;, ~

21~6997 .. . . .

Table 1 - continuation Ex. n Rl R2 (Po~3ition-)R3 Melting No. point ~ C) ,, . . _ , _ ~ .

6 1 ~ c~3 (2-)Cl 9B
F2C~tS ~. ., ~ . :.

7 1 ~ CH3 (3-~Cl 9B

8 I H5C2-CH- CH3 t3-)Cl (~morphous) ~ ;
C~3 `~

9 1 ~ /~ CH3 (4-~Cl 85 -F
/~\ ~ ' ~
1 ~ CH3 t4-)F 104 Il 1 ~ CH3 (4-)Cl 106 ~ ~ :.
12 1 ~ ~ C~3 t4-~OCH3 64 :
~ . .

/~\ .
13 2 ~ CH3 '3'4-'F2 55 f . . ; : .

Le A 29 158-PCT .

` 21~6997 . -- 19 -- `
Table 1 - continuation Ex. n RI R2 (Po~sition-)R3 Melting No. point ~C) ~ ' .
I4 I S CH3 t4-~OCH3 I05 I S CH3 t3-)OCH3 36 I6 I ~ C~13 (3-)CH3 46 I7 I ~ CH3 (3-)CF3 B3 :

I8 O ~ CH3 - 55 19 I ~ CH3 (2-)CI S8 ~ .
ZO O ~ CH3 - 63 Cl '.

2I 1 ~ CH3 ~3-)CF3 48 . CI

22 O CI ~ C~3 - .94 23 I CI ~ CH3 (3-)CF3 98 Le A~ 2 9 15 8 -PCT

i ~13~997 :: -- 20 --Table 1 - continuation Ex. n Rl R2 (Po~ition-)R3 Melting No. point tC) 24 1 ~ CH3 (3-)CF3 25 1 ~ C~3 (~-~Cl 58 26 1 ~ CH3 ~4-)Cl 103 27 1 ~ CH3 ~3-)C~3 69 28 1 F ~ c~3 (3-)OCH3 6S

Z9 1 ~ C~3 (3-)N02 36 30 1 ~ CH3 (3-)CH3 60 .
: : .
31 1 ~ CH3 t3-)CN 90 CH3 _ R3 '`"' '': " ' ', ' ,'' .. ..

. -Le A 29 158-PCT

~ ~13~997 Tabla 1 - continuation Ex. n Rl R2 (Po~ition-)R3 Melting No . point ( C ) ~ .
33 1 ~ C~3~3-)C1 70 34 0 ~ CH3 - 78 1 ~ CH3 t3-)Cl 100 f~\
36 0 ~ CH3 - 43 37 1 $~ c~3 t3-)CF3 89 . ~
38 1 <~ CH3 t 4 ~ ) CH3 l l O

39 1 ~} CH3 t3- )CF3 55 F

` ' ' Le A 29 158-Pt'T ~:

. ~ .. . . .. . . .

~ ~13~9'7 --. 2 2 Table 1 - continuation Ex. n R1 R2 (Po~ition-)R3 ~elting No. point (C) 41 1 ~ CH3 ~3-)C1 84 42 1 ~ CH3 ~3-)CF3 81 43 1 ~ c~3 (4-)CH3 92 44 1 ~ CH3 ~3 )C~3 59 F :`

45 1 F ~ C~3 ~4-)CH3 83 46 1 ~ CH3 (2-~F 62 47 1 ~ CH3 ~3-)F 65 ::

48 1 ~ CH3 t4-)F a7 49 1 ~ c~3 ~4-)OCH3 54 .
:

Le A 2 9 15 8 -PCT

~ ~ 3~ ~97 Tabl~ 1 - continuation Ex. n Rl R2 (Position-)R3 Melting No. point (oc) SO 1 F ~ CH3~4-~N2 125 51 (CH3)3C ~ ~H3 - 69 5Z 1 t~H3)3C ~ CH3 t~-)CH3 (oil) 53 1 tCH3)3C ~ CH3t3-)C1 74 54 1 tCH3)3C ~ CH3t3-)CF3 70 55 H5C2 ~ CH3 - 89 56 1 ~5C2 ~ CH3t3-)CH3 84 57 1 ~5Cz ~ CH313-)C1 89 58 1 H5Cz ~ CH3t3-)CF3 86 59 0 02N ~ CH3 - 156 Le A 29 158-PCT

Table 1 - continuation Ex. n Rl R2 (Position-~R3 Melting ~~ point (C) , .
0 H3C502 ~ CH3 - 199 61 ~3C ~ CH3 - 7~

62 1 ~3C ~ CH3~3-)CH3 102 63 1 H3C ~ CH3(3-)CF3 84 64 H3C ~ C~3 - 61 65 F3C ~ C~3 - 112 66 1 H3C ~ CH3(3-)CF3 82 67 1 H3C ~ CH3(3-~CH3 75 68 1 H3C ~ c~3t3-)C1 88 69 1 H3C ~ CH3t3-)C1 ~5 : .

Le A 29 158-Pt~T
.

~ ~13~997 .

Table 1 - continuation Ex . n Rl R2 ( Po~ition- ) R3 Melting Poin_ ( C) 7~ 1 ~ C~3 ~3-)Cl 54 71 1 ~ CH3 t4- ~Cl 72 72 1 <3 C~3 ~ 3~ ~ C}~3 (oil) 73 1 ~ CH? (4-)CH3 75 Cl~
74 1 ~ CH3 (3-~F 114 ~, Le A 29 158-PCT . -~

` 213~997 Startinq substances of the formula (II):

Example (II~
N_N
~S~NI ICH3 A mixture of 20 g ~0.16 mol) of benzoic acid, 17.2 g (0.16 mol) of 4-methyl-thiosemicarbazide and 250 ml of dioxane is xefluxed and then 25 g (0.16 mol) of phos-phoryl chloride (POCl3) are added dropwise in the course of 45 minutes. After cooling, 230 ml of 13~ strength aqueous sodium hydroxide solution are added, and the mixture is stirred for 2 hours at 20C. It is then diluted with water and, after stirring for 30 minutes, the crystalline product is isolated by filtration.

23.2 g (74% of theory) of 2-methylamino-5-phenyl-1,3,4-thiadiazole of melting point 143C are obtained.

` I

Le A 29 158~PC~

.
~1~6997 .

Use Examples:
Example A

Post-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Test plants which have a height of 5 - 15 cm are sprayed with the preparation of the active compound in such a way as to apply the particular amoullts of active compound de~ired per unit axea. After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.

The figure~ denote:
0~ - no action ~like untreated control) 100% = total destruction `

In this test, a clearly superior activity compared with the prior art is shown, for example, by the compounds of Preparation ~xamples: (9) and (10), the compound of Example (10) also being very well tolerated by beet.

' '.

Le A 29 158-PT

~136997 -- 28 -- .

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~ o u~ ~.
c:
.q ~ u~ ~:
m ~ o o :' ~ .
Q~
o P ~I ~ .
~ ~.¢ U) , _ r~
~q aJ

U

~1 ~ =~u ~,~

Le A 29 158-PCT

-- 29 -- . ;

rl u h o~

,~
~ u~
Q~
c) .' o _, m ,,~ :, :, "
e ~

~ :
:
o ~ UO~
~ o-- .~
~ ~rl .. . .
''~

~ O ¢I~n ~ ~ z ;```:

r~ 3 L

Le A 29 158-PCT ~``~.; .
, .-.~

~,. '~ = `

21.3~9g7 Table A2- Post-emergence test/greenhouse ~:

Active compound Application rate ~eet Mercurialis (g/ha) ,CH2~F

~5~1 - CH3 ~ 10~ 60 10 90 Le A ~9 158-PCT

Claims

Patent Claims:

1. Thiadiazolines of the general formula (I) (I) in which n represents the number 0, 1, 2 or 3, R1 represents C1-C6-alkyl which is optionally sub-stituted by halogen or C1-C4-alkoxy, or repre-sents C3-C6-cycloalkyl or C3-C6-cycloalkyl-C1-C2-alkyl, in each case optionally substituted by halogen and/or C1-C4-alkyl, or represents phenyl, fluorophenyl, difluorophenyl, 2-chlorophenyl, 4-chlorophenyl, bromophenyl, nitrophenyl, cyano-phenyl, 2-methylphenyl, 4-methylphenyl, tri-fluoromethylphenyl, chlorodifluoromethylphenyl, fluorodichloromethylphenyl, bis-trifluoromethyl-phenyl, ethylphenyl, propylphenyl, isopropyl-phenyl, tert-butylphenyl, methoxyphenyl, di-methoxyphenyl, ethoxyphenyl, propoxyphenyl, isopropoxyphenyl, methylthiophenyl, ethylthio-phenyl, methylsulphinylphenyl, ethylsulphinyl-phenyl, methylsulphonylphenyl, ethylsulphonyl-phenyl, difluoromethoxyphenyl, trifluoromethoxy-phenyl, difluoromethylthiophenyl, trifluoromethylthiophenyl, or represents furyl, tetrahydrofuryl, thienyl, tetrahydrothienyl or pyridyl, in each case optionally substituted by halogen, C1-C4-alkyl and/or C1-C4-halogenoalkyl, R2 represents C1-C6-alkyl and R3 represent halogen, cyano, nitro, carboxyl, carbamoyl, or represents C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkoxy-carbonyl, in each case optionally substituted by halogen.

2. Thiadiazolines of the general formula (I) according to Claim 1, characterized in that n represents the number 0, 1, 2 or 3, R1 represents C1-C4-alkyl which is optionally sub-stituted by fluorine, chlorine, bromine, methoxy or ethoxy, or represents C3-C6-cycloalkyl or C3-C6-cycloalkyl-C1-C2-alkyl, in each case option-ally substituted by fluorine, chlorine, bromine, methyl, ethyl, propyl or isopropyl, or represents phenyl, 2-, 3- or 4-fluorophenyl, 2,3-, 2,4-, 2,5-, 3,4-, 3,5- or 2,6-difluorophenyl, 2-chloro-or 4-chlorophenyl, 4-bromophenyl, 2-, 3- or 4-nitrophenyl, 2-, 3- or 4-cyanophenyl, 2-methyl-or 4-methylphenyl, 2-, 3- or 4-trifluoromethyl-phenyl, 3,5-bis-trifluoromethylphenyl, 4-ethyl-phenyl, 4-propylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 2-, 3- and 4-methoxyphenyl, 3,4-dimethoxyphenyl, 4-ethoxyphenyl, 4-methyl-thiophenyl, 4-methylsulphonylphenyl, 2- and 4-di-fluoromethoxyphenyl, 2- and 4-trifluoromethoxy-phenyl, or represents furyl, thienyl or pyridyl, R2 represents C1-C3-alkyl and R3 represents fluorine, chlorine, bromine, cyano, nitro, carboxyl or carbamoyl, or represents C1-C3-alkyl, C1-C3-alkoxy or C1-C3-alkoxy-carbonyl, in each case optionally substituted by fluorine or chlorine.

3. Thiadiazolines of the general formula (I) according to Claim 1, characterized in that n represents the number 0, 1 or 2, R1 represents methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, chloro-methyl, fluoromethyl, dichloromethyl, difluoro-methyl, trichloromethyl, trifluoromethyl, chloro-difluoromethyl, fluorodichloromethyl, chloro-ethyl, fluoroethyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, cyclopropyl, dichloro-cyclopropyl, dimethylcyclopropyl, cyclopentyl, cyclohexyl, phenyl, 2-, 3- or 4-fluorophenyl, 2,3-, 2,4-, 2,5-, 3,4-, 3,5- or 2,6-difluoro-phenyl, 2-chloro- or 4-chlorophenyl, 4-bromo-phenyl, 2-, 3- or 4-nitrophenyl, 2-, 3- or 4-cyanophenyl, 2-methyl- or 4-methylphenyl, 2-, 3- or 4-trifluoromethylphenyl, 3,5-bis-trifluoro-methylphenyl, 2-, 3- or 4- methoxyphenyl, furyl or thienyl, R2 represents methyl and R3 represents fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, trifluoromethyl, methoxy or ethoxy.

4. Process for the preparation of thiadiazolines of the general formula (I) (I) in which n represents the number 0, 1, 2 or 3, R1 represents C1-C6-alkyl which is optionally sub-stituted by halogen or C1-C4-alkoxy, or repre-sents C3-C6-cycloalkyl or C3-C6-cycloalkyl-C1-C2-alkyl, in each case optionally substituted by halogen and/or C1-C4-alkyl, or represents phenyl, fluorophenyl, difluorophenyl, 2-chlorophenyl, 4-chlorophenyl, bromophenyl, nitrophenyl, cyano-phenyl, 2-methylphenyl, 4-methylphenyl, tri-fluoromethylphenyl, chlorodifluoromethylphenyl, fluorodichloromethylphenyl, bis-trifluoromethyl-phenyl, ethylphenyl, propylphenyl, isopropyl-phenyl, tert-butylphenyl, methoxyphenyl, di-methoxyphenyl, ethoxyphenyl, propoxyphenyl, isopropoxyphenyl, methylthiophenyl, ethylthio-phenyl, methylsulphinylphenyl, ethylsulphinyl-phenyl, methylsulphonylphenyl, ethylsulphonyl-phenyl, difluoromethoxyphenyl, trifluoromethoxy-phenyl, difluoromethylthiophenyl, trifluoro-methylthiophenyl, or represents furyl, tetra-hydrofuryl, thienyl, tetrahydrothienyl or pyridyl, in each case optionally substituted by halogen, C1-C4-alkyl and/or C1-C4-halogenoalkyl, R2 represents Cl-C6-alkyl and R3 represents halogen, cyano, nitro, carboxyl, carbamoyl, or represents C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkoxy-carbonyl, in each case optionally substituted by halogen.

characterized in that thiadiazoles of the general formula (II) (II) in which R1 and R2 have the abovementioned meaning, are reacted with aralkyl halides of the general formula (III) (III) in which n and R3 have the abovementioned meaning and X represents halogen, in particular chlorine or bromine, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent.

5. Herbicidal compositions, characterized in that they contain at least one thiadiazoline of the formula (I) according to Claims 1 to 4.

6. Method of combating undesired plants, characterized in that thiadiazolines of the formula (I) according to Claims 1 to 4 are allowed to act on undesired plants and/or their environment.

7. Use of thiadiazolines of the formula (I) according to Claims 1 to 4 for combating undesired plants.

8. Process for the preparation of herbicidal com-positions, characterized in that thiadiazolines of the formula (I) according to Claims 1 to 4 are mixed with extenders and/or surface-active substances.